Certain oxyalkylated derivatives of sucrose



p 1953 M. DE GROOTE 2,652,394

CERTAIN OXYALKYLATED DERIVATIVES OF SUCROSE Filed Feb. 27. 1950 INVENTORPatented Sept. 15, 1953 CERTAIN OXYALKYLATED DERIVATIVES OF SUCROSEMelvin De Groote, University City, Mo., assignor to PetroliteCorporation, a corporation of Delaware Application February 27, 1950,Serial N 0. 146,484

2 Claims.

The present invention is concerned with certain new chemical products,compounds, or compositions which have useful application in variousarts. It includes methods or procedures for manufacturing said newchemical products, compounds, or compositions, as well as the products,compounds, or compositions themselves.

More specifically the present invention is concerned with xylene-solubleoxyalkylated sucrose. The alkylene oxides employed for oxyalkylation arealpha-beta alkylene oxides selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide. In numerous instances the oxyalkylation products arecharacterized only xylene soluble but also water-insoluble. Suchproducts are obtained by the use, at least in part, of an alkylene oxidehaving three or more carbon atoms per oxygen atom such as propyleneoxide. One example of such an oxyalkylated is obtained by reacting 9parts by weight of sucrose with 91 parts by weight of propylene oxide.On the other hand many of the most desirable derivatives are obtained byuse and propylene oxide.

Part of the products herein described, i. e., the oxypropylatedderivatives, specially represent a continuation-in-part of my co-pendingapplication, Serial No. 104,801, filed July 14, 1949, now Patent No.2,552,528.

Briefly stated, the particular invention described in said immediatelyaforementioned copending application is concerned with the breaking ofpetroleum emulsions by means of certain polyol ethers hereinafterdescribed in detail. Such ethers are obtained by treating a watersolublexylene-insoluble polyhydric reactant having at least 4 hydroxyl radicalsand free from any radical having at least 8 uninterrupted carbon atoms,with propylene oxide.

In the aforementioned co-pending application, Serial No. 104,801, filedJuly 14, 1949, one is concerned with an initial material which, likesucrose, is water-soluble and xylene-insoluble. Furthermore, thereactant subjected to oxyalkylation as described in said aforementionedapplication, like sucrose has at least 4 hydroxyl radicals and is freefrom any radical having at least 8 uninterrupted carbon atoms. In saidaforementioned co-pending application the particular reactant employedis propylene oxide, Whereas the instant invention is not so limited.

For convenience, however, reference will be made to the effect ofoxypropylation for the reason that it illustrates one of the sub-generahereby the fact that they are not of both ethylene oxide in described,and also for the reason that it particularly illustrates the effect ofwater solubility.

What is said in aforementioned co-pending application Serial No.104,801, filed July 14, 1949, applies with equal force and effect tosuch subgenus. The followingtext is verbatim: A plurality of propyleneoxide is used in molal ratio tothe hydroxylated reactant so as toconvert the initially water-soluble and xylene-insoluble prodnot in anultimate resultant which is water-insoluble and xylene-soluble. Forinstance, the herein described resultants, or more correctly products ofreaction since they invariably and inevitably represent cogenericmixtures rather than a single component, which mixed with distilledWater so as to give a 5% solution, suspend after a fashion duringvigorous agitation but on being allowed to stand in a quiescent stateimmediately separate out so that within a short length of time, forinstance, within a few minutes to several hours, all or substantiallythe big bulk of material has separated from the aqueous solution orsuspension. In fact, in the higher stages of oxypropylation thematerials obtained seem to go into water at room temperature withconsiderable difliculty and if the water happened to be warm, forinstance at a temperature of 50, or C., the materials were even lesssoluble. An example of a product with vigorous shaking and which, evenso, does not stay dispersed, is the resultant obtained by treating onemole of sorbitol with 200 moles of propylene oxide. Reference as tosolubility is in ordinary cold water at approximately room temperature,for instance, 225 0., or thereabouts. Solubility in xylene refers tosolubility at ordinary temperature and products herein specified aresoluble in xylene so as to form a 5% solution readily.

In the present invention one is not limited to the use of propyleneoxide but one may use oxides which introduce a more concentratedhydrophile character, such as ethylene oxide or glycide. Indeed, suchproducts may show solubility in both xylene and water. This Will beillustrated by subsequent examples. Thus, it is noted that in thebroadest aspect the invention is concerned with xylene-soluble productswhether water-soluble or not.

The compounds or cogeneric mixtures herein described are not only usefulfor breaking oil field emulsions but also are useful for various otherpurposes, such as a break-inducer in the doctor treatment of sourhydrocarbons, as an emulsifying agent, as a component in theprepdiificult to disperse even state throughout the oil whichconstitutes the continuous phase of the emulsion.

This specific application or use of reagents is described and claimed inco-pending application, Serial No. 146,483, filed February 27, 1950, nowPatent No. 2,602,051, gra ted July 1, 1952.

For convenience, what is said hereinafter is divided into two parts:

Part 1 will be concerned with the description of the oxyalliylation ofsucrose, an

Part 2 will be concerned with derivatives valuable for various purposesincluding demu lsification but not specifically claimed in the instantcation. apPli PART 1 The oxyalkylation of sucrose can be conducted byvarious procedures. My preference is to preare a slurry of finelypowdered sugariconfectionery sugar) and xylene, add an alkaline catalystto theextent of about /2 70 to 3% and proceed with the oxyalsylation inabsence of water. The alkaline catalyst employed may be any one of thecustomary catalysts such as sodium metriylate, caustic soda, causticpotash, etc. Confectionery sugar usually contains about 3% of starch. Itis possible that this combines at the tem erature, of oxyalkylation orit may be there is an insignificant decomposition of sugar itseli. Inany event, in the early stages of oxyalkylat on there is frequently aslightly amber tinge due to. caramelization or decolorization of starchwhich, however, becomes more diluted on addition of the alkylene o-Xide.Such color can be removed in the usual manner with filtering charcoals,deco-lorizing clays, etc. For the magority ofindustrial purposes,however, this color is immaterial. Similarly, the solvent which ispresent,

h a X lene, can be removed if desired. listiilati on, particularlyvacuum distillation, can be employed. Heraagain, it is immaterialwhether the solvent is removed or not when used for most industrialpurposes.

I have prepared a number of derivatives from sucrose varying from a fewhundred grams or less in the laboratory to substantially larger amounts.In preparing a large number of examples I have found it particularlyadvantageous to use laboratory equipment which permits continuousoxypropylation and oxyethylation. More specific reference will be madeto treatment with glycide subsequently in the text.

The oxypropylation step is, of course, the same as the oxyethylationstep insofar thattwo low boiling liquids are handled in each instance.What immediately follows refers to oxyethylation and it is understoodthat oxypropylation can be handled conveniently in exactly the samemanner.

The oxyethylation procedure employed in the preparation of sucrosederivatives has been uniformly the same, particularly in light of thefact that a continuous operating procedure was employed. In thisparticular procedure the autoclave was a conventional autoclave, made ofstainless steel and having a capacity of approximately one gallon, and aworking pressure of 1,000 pounds gauge pressure. The autoclave wasequipped with the conventional devices and openings, such as thevariable stirrer operating at speeds from 50.1%. P. to 500R. P. M.,thermometer well and thermocouple for mechanical thermometers; emptyingoutlet; pressure gauge, manual ventline; charge hole for initialreactants; at least one connection for conducting the incoming alkyleneoxide, such as ethylene oxide, to the bottom of the autoclave; alongwith suitable devices for both cooling and heating the autoclave,such'as. a cooling jacket and, preferably, coils in addition thereto,with the jacket so arranged that ity is suitable for heating with steamor cooling'with water, and further equipped with electrical devices.Such autoclaves are, of course, in essence small scale replicas of theusual conventional autoclave used n oXyalkylation procedures.

Continuous operation, or substantially continuous operation, is achievedby the use of a separate container to hold the alkylene oxide beingemployed, particularly ethylene oxide. The container consistsessentially of a laboratory bomb having a capacity of about one-halfgallon, or somewhat in excess thereof. This bomb was equipped, also,with aninlet for charging, and an outlet tube going to the bottom of thecontainer so as to permit discharging of alkylene oxide in the liquidphase to the autoclave. Other conventional equipment consists, ofcourse, of the rupture disc, pressure gauge, sight feed glass,thermometer connection for nitrogen for pressuring bomb, etc. The bombwas placed on a scale during use and theconnections between the bomb andthe autoclave were flexible stainless hose or tubing so that continuousweighings could be made without breaking or making any connections. Thisalso appliedto the nitrogen line, which was used to pressure the bombreservoir. To the extent that. it. was required, any other usualconventional procedure or addition which provided greater safety wasused, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxyethylations becomeuniform in that the reaction temperature could be held within a fewdegrees of any selected point in this particular range. In theearly-stages where the concentration of catalyst is high the temperaturewas generally set for around C. or thereabouts. Subsequentlytemperatures up to 170 C. or higher may be required. It will be noted byexamination of subsequent examples that this temperature range wassatisfactory. In anycase, where the reaction goes more slowly a highertemperature may be used, for instance, C. to 180 C., and if need be 185.C. to 190 S. Incidentally, oxypropylation takes place more slowly thanoxyethylation as a rule and for this reason we have used a temperatureof approximately C. to C., as being particularly desirable for initialoxypropylation, and have stayed within the range of 165 C. to 0., almostinvariably during oxypropylation. Ihe ethylene oxide was forced in bymeans of nitrogen pressure as rapidly as it was absorbed as indicated bythe pressure gauge on the autoclave. In case the reaction slowed up thetemperature was raised so, as to speed up the reaction somewhat by useof extreme heat. If need be, cooling water was employed to control thetemperature.

As previously pointed out in the case of oxypropylation asdiiferentiated from oxyethyla tion, there was a tendency for thereaction to slow up as the temperature dropped much below the selectedpoint of reaction, for instance, 170

C. In this instance the technique employed was the same as before, thatis, either cooling water was cut down or steam was employed, or theaddition of propylene oxide speeded up, or electric heat used inaddition to the steam in order that the reaction proceeded at, or near,the selected temperature to be maintained.

Inversely, if the reaction proceeded too fast regardless of theparticular alkylene oxide, the amount of reactant being added, such asethylene oxide, was cut down or electrical heat was cut off, or steamwas reduced, or if need be, cooling water was run through both thejacket and the cooling coil. All these operations, of course, aredependent on the required number of conventional gauges, check valves,etc., and the entire equipment, as has been pointed out, is conventionaland, as far as I am aware, can be furnished by at least two firms whospecialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory or semi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing: (a) If prepared from glycerol monochlorohydrin, this productshould be comparatively pure; (1)) the glycide itself should be as pureas possible as the effect of impurities is diflicult to evaluate; (c)the glycide should be introduced carefully and precaution should betaken that it reacts as promptly as introduced, i. e., that no excess ofglycide is allowed to accumulate; (d) all necessary precaution should betaken that glycide cannot polymerize per se; (e) due to the high boilingpoint of glycide one can readily employ a typical separatable glassresin pot as described in the co-pending application of Melvin De Grooteand Bernhard Keiser, Serial No. 8,822, filed February 16, 1948, andoffered for sale by numerous laboratory supply houses. If sucharrangement is used to prepare laboratory scale duplications, then careshould be taken that the heating mantle can be removed rapidly so as toallow for cooling; or better still, through an added opening at the topthe glass resin pot or comparable vessel should be equipped with astainless steel cooling coil so that the pot can be cooled more rapidlythan mere removal of mantle. If a stainless steel coil is introduced itmeans that conventional stirrer of the paddle type is changed into thecentrifugal type which causes the fluid or reactants to mix due toswirling action in the center of the pot. Still better, is the use of alaboratory autoclave of the kind previously described in this part; butin any event, when the initial amount of glycide is added to a suitablereactant, such as sorbitol, the speed of reaction should be controlledby the usual factors, such as (a) the addition of glycide; (b) theelimination of external heat, and (0) use of cooling coil so there is noundue rise in temperature. All the foregoing is merely conventional butis included due to the hazard in handling glycide.

Example 1b ing, heat control, stirrer, inlet, outlet, etc., which isconventional in this type of apparatus. The capacity was approximately3% liters. The stirrer operated at a speed of approximately 250 R. P. M.There were charged into the autoclave 460 grams of powdered sugar(containing 3% corn starch) 300 grams of xylene, and 15 grams of sodiummethylate. The autoclave was sealed, swept with nitrogen gas andstirring started immediately and heat applied. The temperature wasallowed to rise to approximately 150 C. At this particular time theaddition of propylene oxide was started. It was added continuously atsuch speed that it was absorbed by the reaction as added. The amountadded in this operation was 1350 grams. The time required to add thepropylene oxide was two hours. During this period the temperature wasmaintained at 150 to 180 0., using cooling water through the inner coilswhen necessary and otherwise applying heat if required. The maximumpressure during the reaction was pounds per square inch. Ignoring thexylene and sodium methylate and considering the starch a sugar forconvenience, the resultant product represent approximately one-fourthsugar and three-fourths propylene oxide. More exactly, the figures areas follows: Sugar 21.8%; propylene oxide 64.0%; and xylene 14.2%. Theproduct, unlike the initial product, was xylene-soluble andwater-emulsifiable.

Example 2b The same procedure was followed as in Example lb, preceding,except that the initial prod not was the one identified as Example 112,preceding. 703 grams of this material, excluding xylene, werechargedinto the autoclave. Acutally there were present 116 grams of xyleneresidual from the previous example. The 703 grams of reactantrepresented originally 179 grams of sugar and 524 grams of propyleneoxide. To this there were added 8 grams additional of sodium methylateand then 250 grams of ethylene oxide. The ethylene oxide was added inthe same manner as propylene oxide but, being more reactive, acted morerapidly. The 250 grams reacted in five minutes time with a temperaturevarying from to C., with a maximum pressure of 150 pounds per squareinch. At the end of this time, ignoring sodium methylate as before, thecomposition on both a xylene-conltaining basis and a xylene-free basis,was as folows:

The resultant'product was both water and xylene-soluble.

Example 31) The same procedure was followed as in Example 2b, preceding,i. e., the initial reactant was the product identified as Example 15.788 grams of this material were taken, representing 172 grams ofsucrose, 504 grams propylene oxide, and 112 grams xylene. To this therewere added 8 grams of sodium methylate and then 1225 grams of propyleneoxide in the same manner as in Example 1b. The time required wasconsiderably less in proportion, to wit, 30 minutes.

of this time the temperature of operationwas between to 200 C.,

Sugar: 4.3 4.2 Propylene Oxide 7 93: Xylene .2. 8

aesaeea *Percent =Percent gar Propylene Oxide Xylene I he product waswater-insolube.and xylene-soluble.

Example 4b 'The reactant employed was the end .product in Example 3b,preceding. The autoclave was charged with 759 .grams of this material,representing 64.5 grams of sucrose, 552 ,grams of propyleneoxideandAZldgra-msrif xylene. 1N0. sodium methylate wasa'ddediin thisparticular operation. 270 grams of ethylene oxide were added in themanner described previously in "foregoing .examples. The ethylene oxidereacted within a ten-minute period. The maximum temperature was 170 C.,and the maximum pressure was 150 pounds per square inch. The compositionof the resultant .product onlboth the xylene-containing and the.xylene-free lbas'is is .shown in the following table:

' Percent Percent 'The product Was=b'oth water-soluble andxylenesoluble.

Example 512 The initial reactant employed was .the product previouslydescribed'as Examplefib. I768 gramsof this material were chargediintothe autoclave. This was equivalent 'to 65 grams sucrose, "6.66 grams ofpropylene'oxide,.and43 gramsof xylene. N0 addition of so'dium-methylatewas made this operation. 'There were .employed'in the oxyalkylation "785.grams of propylene oxide. "The time requiredto add this, propyleneoxide was 130 minutes. "Thetemperature varied from 150 .C. to 185 C. Themaximum gauge pressure was 200 pounds per square inch. The compositionof the product on a xylene-containing and a xylene-free basis was asfollows:

Percent :Percent The product was xylene-soluble and water-insoluble.

.Esmmple- 6b previously with 232 grams of "ethylene oxide. No sodiummethylate was added during'thispperation. The time required to addtheethylene oxide was 30' minutes. The'maximum temperature during thisoperationwas 170"C. "The maxi Percent Percent "The product was both"water-soluble .and zxyle'nesoluble. I

Example 7b .The procedure employed was the same as in the previousexampleland thereactant employed, .as in the previous example, was theproduct ,previousl-y identified as Example '51). 594 grams .of produce,Example .'5b, were used. This represented.25;grams of sucrose, i552grams of'propylene oxide, and.17 .grams of xylene. To this there wereadded 495 grams of propylene oxide. There was no catalyst added duringthis operation. One result was that the-operation went fairly slowly.and required-six hours at a maximum temperature of .175 .C.,.and amaximum pressure-of .2510 pounds .per square .inch. .The composition ofthe .final product is shown in the fol1owing:table:

.Percent Percent "This product was water-insoluble and possiblycoul'd'be considered as water-dispersible to a'degree. It wasxylene-soluble.

J Following "the same procedure "I have prepared a large number ofderivatives from sucrose which were xylene-soluble. I have usedpropylene oxide in substantially every instance either alone or in"combination with ethylene oxide 'or glycide. Butylene oxide, except forits cost, of course, 'could be used to replace propylene-oxide 'mole"formole withlessrequired to givethesameeffect.Subsequentreferencewill-be made to the figure which is a conventionalrepresentation-of compositions involvin'g sucrose, ethylene oxide andpropylene oxide. Theiollowing-table is-a-sum- 'maryofjpart' of'theproducts'prepared:

Example:No. Sucrose gggg g l Percent4 Percent Percent It will be notedthat Examples 17.) to 7b, in-

-'elus'ive, correspondtothose described in greater the presence ofsodium methylate as a catalyst to the extent of about 1% to 3% of thevarious oxyalkylations. The initial operation was started at 150 and thetemperature of reaction varied from 150 to 200 C. as the maximum.Usually maximum pressure during oxypropylation was not over 260 poundsper square inch but in some instances was as high as 250 pounds persquare inch. Thus, the pressure range was from 150 pounds per squareinch up to 250 pounds per square inch. In all these experiments wherepropylene oxide and ethylene oxide both were added the propylene oxidewas added first and then the ethylene oxide.

In a second series of examples where both propylene oxide and ethyleneoxide were used, the procedure was to add ethylene oxide first and thenpropylene oxide.

Finally, the same series of examples were repeated, using randomoxyalkylation as far as the ethylene oxide and propylene oxide wereconcerned, i. e., the two products were mixed in the predeterminedproportion to give the composition desired and oxyethylation andoxypropylation allowed to take place simultaneously and in a randomfashion.

Example 22b The same piece of equipment was used as previouslydescribed, i. e., an autoclave, although in the instant experimentinvolving the use of glycide there was no pressure involved and certainchanges were made as noted subsequently. The autoclave was equipped witha water-cooled condenser which was shut off when used as an autoclave.It was equipped also with a separatory funnel and an equalizing pressuretube so that liquid, such as glycide, could be fed continuously at a'dropwise or faster rate into the vessel and the rate was controlled byvisual examination. For convenience, this piece of equipment is referredto as an autoclave becauseit was designed essentially for such use butit is to be noted it was not so used when glycide was employed as thealkylene oxide.

There were charged into'the autoclave the same reactants (sucrose,xylene and sodium methylate) as in Example 1b. The autoclave was sealed,swept with nitrogen gas and started immediately and heat applied. Thetemperature was allowed to rise to 120 C. The glycide employed wascomparatively pure. Over a period of 2% hours, 230 grams of glycide wereused. This was charged into the upper reservoir vessel which had beenflushed out previously with nitrogen and was the equivalent of aseparatory funnel. The glycide was started slowly into the reaction massat a dropwiser'ate. The reaction started immediately and the temperaturerose approximately 12 to 18 C. "Cooling water was run through the coilsso the temperature for addition of glycide was controlled within therange roughly of 112 to 133 C. This reaction took place at atmosphericpressure with simply a small stream of nitrogen passing into theautoclave at the very top and passing out of the open condenser so as toavoid any possible entrance of air. The product at all times,particularly when the xylene was evaporated, was water-soluble. Thisproduct was subsequently subjected to oxypropylation so as to introducesufficient propylene oxide so that the final product on axylene-freebasis represented sucrose 4% byweight, glycide 2% by weight, andpropylene oxide 94% by weight, g

Needless to say that glycide can be introduced in any other mannersuggested by previous examples, for instance, the product can beoxypropylated first and glycide used in place of ethylene oxide, usingabout one-half to threefourths the weight of glycide to replace apredetermined weight of ethylene oxide; or for that ,matter at any pointwhere ethylene oxide is being used part of the ethylene oxide can bereplaced by glycide.

In addition to ethylene oxide, propylene oxide, glycide, or mixtures ofthe two, or all three of these oxides, one can use also methyl glycideand butylene oxide. Butylene oxide, if employed at all, should be usedin combination with ethylene oxide, glycide or methyl glycide. The mostdesirable combination is, of course, one in which the oxyalkylatedderivative shows marked surface activity which can be readily detectedby an emulsification test as explained in the text immediatelyfollowing.

The most desirable derivatives appear to be those which have not onlythe solubility characteristics previously described but have ahydrophile-hydrophobe balance so as to give them the property of anemulsifier at least to a significant degree.

To determine such preferred hydrophile-hydrophobe balance all that oneneed do is have a xylene solution within the range of 50 to parts byweight'of xylene and mix such solution with one, two or three times itsvolume of distilled water and shake vigorously so as to obtain anemulsion which may be ofthe oil-in-water type or the water-in-oil type(usually the former) but, in any event, is due to thehydrophile-hydrophobe balance of the oxyalkylated derivative. I prefersimply to use the xylene diluted derivatives, which are described else-.where, for this test rather than evaporate the solvent and employ anymore elaborate tests.

Reference is made to the hereto attached figure which is presented inconventional manner showing the compounds derived from variouscombinations of sucrose and ethylene oxide, sucrose and propylene oxide,,or sucrose and both ethylene and propylene oxides. It is to be noted inthe hereto appended claims that the invention is not concerned withwater-soluble derivatives as, for example, oxyethylated sucrose. It isconcerned with such derivatives in which the hydrophile character ofsucrose has been radically altered so that the derivative isxylene-soluble. In a more restricted sense the invention is concernedwith types of oxalkylated derivatives which are both xylene-soluble andwater-soluble. Furthermore, a number of such derivatives show preferredhydrophobe-hydrophile balance as indicated by a simple emulsificationtest. My preferred reagents come within the approximate trapezoidal areadefined by points I, 2, 3,

' and i on the accompanying figure.

It is obvious, of course, that minor variations can be madewithoutdetracting from the spirit of the invention. For instance, one hydroxylor two hydroxyls of sucrose could be converted into acetate groups. Asanother variant, in addition to the oxides enumerated, one might injectone or more moles of some other alkylene oxide such as-methyloxy-2,3-opoxypropane, l-ethyloxy-Z, 3-epoxypropane, and1-propyloxy-2, 3-2-poxypropane. Such obvious variants in such a'largemolecule would have little or no efiect in changing the generalcharacteristic property, 1. e., hydrophobe-hydrophiie balance, xylenesolubility and water and xylene solubility, etc. Such obvious variantswhich do not detract from the significant characteristics and propertiesare all within the scope of the instant invention.

For reasons which are obvious it is substantially impossible to useconventional methods and obtain a single glycol ether from even amonohydric reactant or its equivalent. The reactant herein employed andsubjected to oxyalkylation is polyhydric which means that the situationis even more complicated. Actually one obtains a cogeneric mixture ofclosely related or touching homologues. These materials invariably havehigh molecular weights and cannot be separated from one another by anyknown method without decomposition. The properties of such a mixturerepresent the contribution of various individual members of the mixture.

Even if one were concerned with the monohydric reactant one cannot drawa single'fornlula and say that by following such and such procedure onecan readily obtain 80% or 90% or 100% of such compound. However, in thecase of at least monohydric initial reactants one can readily draw theformulas of a large number of compounds which appear in some of theprobable mixtures or can be prepared as components and mixtures whichare manufactured conventionally. In the instant case where one isconcerned with the polyhydric reactant there is little or nothing to begained by compiling and including such variety of possible formulas.

Simply by way of illustration reference is to the copending applicationof De Groote, Wirtel and Pettingill, Serial No. 109,791, filed August11,1949.

However, momentarily referring again to a monohydric initial reactant itis obvious that if one selects any such simple hydroxylated con..- poundand subjects such compound to oxyalkylation, such as oxyethylation, oroxypropylation, it becomes obvious that one is really producing apolymer of the alkylene oxide except for the terminal group. This isparticularly true wher the amount of oxide added is comparatively large,for instance, 10, 20, 3'0, 40,or 50 units. If such a compound issubjected to oxyethylation so as to introduce units of ethylene oxide,it is well known that one does not obtain a single constituent, which,for the sake of convenience, may be indicated as RO(C2H4O)nOH. Instead,one obtains a cogeneric mixture'c-i closely related homologues, in whichthe formula may be shown as the following: RO(C2H4O)11H, wherein as faras the statistical average goes, is 30, but the individual memberspresent in significant amount may vary from instances where n has avalue of 25, and perhaps less, to a point where 11. may represent ormore. Such mixture, is,"as stated, a cogeneric closely related series oftouching homologous compounds. Considerablev investigation has been madein regard to the distribution curves for linear polymers. Attention isdirected to the article entitled Fundamental principles of condensationpolymerization, by Paul J. Flory, which appeared in Chemical Reviews,volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators,there is no satisfactory -mthod, based on either experimental ormathematical examination, of indicating the exact proportion of thevarious members of touching homologous series which appear in 'cogenericcondensation products of the kind described. This" means that from thepracticalstandpoi-nt,

i. e., the ability to describe how to make the product underconsideration and how to repeat such production time after time withoutdifiiculty, it is necessary to resort to some other method ofdescription.

Actually from a practical standpoint, and particularly in regard to thesub -gems illustrated 'b' the figure, it is much more satisfactory todescribe the ultimate composition in terms of the reactants, i. e.,sucrose and propylene oxide, 0:: sucrose and both propylene oxide andethylene oxide. The reason for this statement is obvious and again, forfurther discussion of the principle involved, reference is made totheaforementioned De Groote, Wirtel and Pettingill co-p'ending application.

For sake of preserving a line of demarcation from another inventionwhich may or may not involve sucrose and involves alkylene oxides, suchas propylene oxide particularly, I direct attention to the following.Allyl sucrose can be prepared so as'to have approximately 3 to 6 allylradicals per sucrose molecule. See Zie'f and Yanovslzy, Ind. Eng. Chem,vol. 41, p 1697 (1949).

Similarly, one can prepare allyl starch and allyl dextrine. I have foundthat if allyl sucrose is polymerized, particularly by blowing with so asto yield a viscous liquid or one which is not only viscous but alsostringy, or one which is polymerized even further so that even a 50%solution in xylene is stringy, that such material can be treated with analkylene oxide, particularly propylene oxide, or propylene and ethyleneoxide, in exactly the same manner as herein described, to yield productswhich are valuable for all the purposes herein described in regard tosucrose derivatives, and particularly valuable for demulsification. Suchallyl sucrose, or other allyl carbohydrates can be polymerized alone orcopolymerized with other allyl-containing derivatives which may, or maynot be hydroxylated, such. as glycerol alpha-allyl ether, tri-allylether of glycerol, the di-allyl ether of glycerol, compounds obtained bytreating allyl alcohol with several moles of glycide, and particularly avariety of materials such as those described in U. S. Patent No.2,4502%, dated September 28, 1945, to and Sholral, and U. S. Patent No.2,336,633, dated December 7, 1943, to Griin and Stoll. oi such examplesare free from any radical, at least prior to polymerization,- havingmore than '2' carbon atoms. A number are Water-soluble prior topolymerization or even thereafter. However, copolymerization can take.place' between allyl sucrose and allyloleate, allyl ricinoleate; orwith total and fractional esters derived from detergent-formingmonocarboxy acids having 8 to carbon atoms, such as higher fatty acids,naphthenic acids, abietic acids, and the allyl ether of glycerol,diglycerol, or diallyl ether of glycerol: and polycarboxy acids can beemployed also in preparation of various allyl derivatives suitable forpolymerization or co-polymerization. As previously stated theoxyalkylation derivatives which are analogous to the sucrose derivativesherein described constitute an entirely separate invention and; at notincluded herein.

PART 2 Attention is directed to the fact that the herein describedcompounds, compositions and the, like which are particularly adapted foruse as demulsifiers for water-in-oil emulsions as found in the petroleumindustry are hydroxylate'd derivatives, i. e., carry or include aterminal hydroxyl radicalas part of their structure. I have found 13that if such hydroxylated compound or compounds are reacted further soas to produce entirely new derivatives, such new derivatives have theproperties of the original hydroxylated compound insofar that they areeffective and valuable demulsifying agents for resolution ofWater-in-oil emulsions as found in the petroleum industry, as breakinducers in doctor treatment of sour crude, etc.

Such hydroxylated compounds canbe treated with various reactants such asglycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleicanhydride, ethylene imine, etc. If treated with epichlorohydrin ormonochloroacetic acid the resultant product can be further reacted witha te tiary amine such as pyridine, or the like, to give quaternaryammonium compounds. If treated with maleic anhydride to give a totalester the resultant can be treated with sodium bisul'fite to yield asulfosuccinate. Sulfo groups can be introduced also by means of asulfating agent as previously suggested, or by treating the chloroaceticacid resultant with sodium sulfite.

However, the class of derivatives most readily prepared in wide varietyare the esters of monocarboxy and polycarboxy acids.

Assuming a typical derivative which can be indicated thus:

RO(CaHO)n(C2H4O)n'H the ester of the monocarboxy acid is as follows:

aowanioproznlopu a' The acid ester of a dicarboxy acid is as follows:

The complete ester of a dicarboxy acid is as follows:

The quaternary compound obtained by reacting the above-mentioned productwith pyridine is as follows:

Among the various kinds of monocarboxy acids suitable for preparation ofesters arethe alpha halogen monocarboxylic acids having not over 6carbon atoms. Typical acids exemplifying this class are chloroaceticacid, dichloroacetic acid, bromoacetic acid, alphabromobutyric acid,etc.

Needless to say, in this instance and all others Cir have residualhydroxyl radicals or residual carboxy radicals, but also partial estersin which both are present.

A somewhat similar type of ester is obtained from hydroxy acetylateddrastically-oxidized castor oil fatty acids. It is to be pointed outthat hydroxy acetylation may take place first, and drastic oxidationsubsequently, or the reverse may be true, or both procedures may beconducted simultaneously. In any event, such products supply acylradicals of one type of ester herein included.

Another somewhat similar class are esters obtained from hydroxyacetylated drasticallyoxidized dehydrated ricinoleic acid. In this classricinoleic acid, castor oil, or the like, is subjected to dehydration asan initial step. Such products may be employed to supply the acylradical of one type of ester herein included.

Another type of ester which may be employed is a sulfo fatty acid esterin which there is present at least 8 and not more than 22 carbon atomsin the fatty acid radical. The sulfo radical includes both the acidsulfonates and the sulfonic acids. Briefly stated, suitable sulfo acidsherein employed as reactants are sulfo oleic, sulfo ricinoleic, sulfoaromatic fatty acids obtained, for example, from benzene, toluene,xylene, etc., and oleic acid or some other unsaturated acid.

Another class of acids are polycarboxy acids such as commonly used informing plasticizers, polyester resins, etc. One may use a tricarboxyacid, such as tricarballylic acid, or citric acid, but my preference isto employ a dicarbcxy acit, or acid anhydride, such as oxalic acid,maleic acid, tartaric acid, citraconic acid, phthalic acid, adipic acid,succinic acid, azeleic acid, sebacic acid, adduct acids obtained byreaction between maleic anhydride and cltraconic anhydride, and eitherbutadiene or cyclopentadiene. Oxalic acid is not quite as satisfactory.as some of the other acids, due to its tendency to decompose. In lightof raw material costs it is my preference to use phthalic anhydride,maleic anhydride, citraconic anhydride, diglycollic acid, adipic acidand certain other acids in the same price range which are both cheap andheat-resistant. One may also use adduct acids of the diene or cloclrertype.

Another class of esters are derived from certain high, molal monocarboxyacids. It is well known that certain monocarboxy organic acidscontaining 8 carbon atoms or more, and not more than 32 carbon atoms,are characterized by the fact that they combine with alkalies to producesoap or soaplike materials. These detergentforming acids include fattyacids,,resin acids,

petroleum acids, etc. ,For the sake. of convenience, these acids will beindicated by the formula R.COOH., Certain derivatives ofdetergent-forming acids react with alkali to produce soap or soaplikematerials and are the obvious ,equivalent of the unchanged or unmodifieddetergent-forming acids. For instance, instead of fatty acids one mightemploy the chlorinated fatty acids. Instead of the resin acids, onemight employ the hydrogenated resin acids. Instead of naphthenic acids,one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fattyacids; and, of course, this is also true in regard to derivatives of thekind indicated, insofar that such derivatives are obtained from higherfatty acids. The petroleum acids include not. only naturally-occurringnaphthenic acids, but also acids obtained by the oxidation of wax,paraffin, etc. Such acids may have as many as 32 carbon atoms. Forinstance, see U. S. Patent No. 2,242,837, dated May 20, 1941, toShields.

The monocarboxy detergent-forming esters of the oxyalkylated derivativesherein described, are preferably derived from unsaturated fatty acidshaving 18 carbon atoms. Such unsaturated fatty acids include oleic acid,ricinoleic acid, linoleic acid, etc. One may employ mixed fatty acidsas, for example, the fatty acids obtained from hydrolysis of cottonseedoil, soybean oil, etc. It is my ultimate preference'that the esters ofthe kind herein contemplated be derived from unsaturated fatty acids,and more especially, unsaturated fatty acids containing a hydroxylradical, or unsaturated fatty acids which have been subjected tooxidation. In addition to synthetic car-boxy acids obtained by theoxidation of paraffins or the like, there is the somewhat analogousclass obtained by treating carbon dioxide or carbon monoxide, in thepresence of hydrogen or an olefine, with steam, or by causinga'halogenated hydrocarbon to react with potassium cyanide andsaponifying the product obtained. Such prod ucts or mixtures thereof,having at least 8 and not more than 32 carbon atoms, and having at leastone carboxyl group or the equivalent there of, are suitable asdetergent-forming monocarboxy acids; and another analogous class equallysuitable is the mixture of carboxylic acids obtained by the alkalitreatment of alcohols of high molecular weight formed in the catalytichydrogenation of carbon monoxide.

One may have esters derived not only from a single class of acids of thekind described, but

also from more than one class, i. e., one-may employ mixed esters suchas esters obtained, for example, from high molal detergent-formin acidshaving 8 to 22 carbon atoms, as previously described, in combinationwith acids of the alpha halogen carboxy type having less than 8 carbonatoms, such as chloroacetic acid, bromoacetic acid, etc., as previouslydescribed.

Drastically-oxidized oil, such as drasticallyoxidized castor oil, ordrastically-oxidized de-" hydrated castor oil, may be employed to supplythe acyl radical. In other instances, one may produce mixed esters byusing polycarboxy acids, such as phthalic acid, diglycollic acid, etc.,in combination with detergent-forming acids, such as oleic acid, stearicacid, naphthenic acid, etc. Other carboxy acids may be employed in whichthere is also a sulfo group present, such as sulfo phthalic, sulfobenzoic, sulfo succinic, etc. Esters may be obtained from low molalhydroxylated acids having less than 8 carbon atoms, such ashydroxyacetic acid, lactic acid, etc. Similarly, one mayemploy low molalaliphatic acids having less than 8 carbon atoms, such as acetic acid,butyric acid, etc. Similarly, one may employ low molal acids having thevinyl radical, such as acrylic acid, methacrylic acid, crotonic acid,etc. It will be noted that these acids contain various numbers of acylradicals varying generally up to 22 carbon atoms for the monocarboxyacids, and as many as 36 carbon atoms in the case of certain polycarboxyacids, particularly the dimer obtained by the dimerization of9.11-octadecandienic acid. As to this particular product, see U. S.Patent No. 2,347,562, dated April 25, 1944, to Johnston.

Other suitable acids are cyclic monocarboxy acids having not over 32carbon atoms. Examples of such acids include cyclohexane acetic acid,cylohexane butyric acid, cyclohexane propionic acid, cyclohexane caproicacid, benzoic acid, salicylic acid, phenoxy acetic acid, etc.

The preparation of such esters are conven tional and do not requireelaborate description. Generally speaking, my procedure is to react theappropriate amount of a selected hydroxylated compound with the freeacid in presence of a high boiling solvent, such as xylene, using 1% or2% of para-toluene sulfonic acid along with a phase-separating trapuntil the amount of water indicates the reaction is complete, orsubstantially complete. The time required is usually 4 to 20 hours. Suchesters are, as previously stated, very effective for resolution ofwater-in-oil emulsions as found in the petroleum industry.

Having thus described my invention what I claim as new and desire tosecure by Letters Patent, is:

1. Hydrophile synthetic products, said hydrophile synthetic productsbeing xylene soluble; said hyprophile synthetic products beingoxyalkylation products of sucrose with at least one alkylene oxide ofthe class consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methyl glycide, at least part of the alkylene oxide beingselected from the class consisting of propylene oxide and butyleneoxide, the proportion of sucrose radical in such product being less than10% '(weight basis) of the total on the assumption of completeness ofreaction and on the average statistical basis.

2. Products of claim 1 with the proviso that the alkylene oxideconstituent include both ethylene oxide and propylene. oxide and thatthe relative proportions of the sucrose, ethylene oxide and propyleneoxide be within the ranges of about 2 to about 7% sucrose, about 23 toabout ethylene oxide, and about 23 to about 17062; propylene oxide, thetotal of the three being MELVIN DE GROOTE.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Le Maistre et al.: J. Org. Chem. 13 (1948), pp.

1. HYDROPHILE SYNTHETIC PRODUCTS, SAID HYDROPHILE SYNTHETIC PRODUCTSBEING XYLENE SOLUBLE; SAID HYPROPHILE SYNTHETIC PRODUCTS BEINGOXYALKYLATION PRODUCTS OF SUCROSE WITH AT LEAST ONE ALKYLENE OXIDE OFTHE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDEGLYCIDE AND METHYL GLYCIDE, AT LEAST PART OF THE ALKYLENE OXIDE BEINGSELECTED FROM THE CLASS CONSISTING OF PROPYLENE OXIDE AND BUTYLENEOXIDE, THE PROPORTION OF SUCROSE RADICAL IN SUCH PRODUCT BEING LESS THAN10% (WEIGHT BASIS) OF THE TOTAL ON THE ASSUMPTION OF COMPLETENESS OFREACTION AND ON THE AVERAGE STATISTICAL BASIS.